Diacetylene compound having double bond and shaped article thereof

ABSTRACT

Disclosed is a diacetylene compound comprising, as structural units, (a) at least one member selected from diacetylene group-containing organic groups of the formulae (I) and (II): 
     
         R.sup.I --C.tbd.C--C.tbd.C--R.sup.II --                    (I) 
    
     and 
     
         --R.sup.III --C.tbd.C--C.tbd.C--R.sup.IV --                (II) 
    
     wherein R I  is hydrogen or a (C1-16) monovalent organic group, and R II , R III  and R IV  are a (C1-13) divalent organic group, 
     (b) at least one organic group having at least one carbon-to-carbon double bond, and (c) at least one connecting group connecting the units (a) and (b) , which connecting group is selected from amide, imide, ester, ether, amino, imino, urethane, sulfonyl and carbonyl bonds. A cured shaped article made of this compound exhibits isotropically a high elastic modulus and has excellent mechanical properties.

This is a continuation of application No. 07/484,005, filed Feb. 23,1990, now U.S. Pat. No. 4,987,257, which is a FWC of 07/363,330 filedJun. 7, 1989, now abandoned, which is a FWC of 07/032,445 filed Mar. 31,1987, now abandoned.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

The present invention relates to a diacetylene compound having at leastone double bond, which has excellent curing reactivity and provides ashaped article having a high elastic modulus, and to a shaped articlethereof.

(2) Description of the Related Art

As the thermosetting resin, a phenolic resin, an epoxy resin, anunsaturated polyester resin and other resin are known. However, curedshaped articles obtained from these resins have an elastic modulus of 4to 5 GPa at highest. Therefore, when these resins are utilized asmaterials having high strength and high elastic modulus, they are usedas fiber-reinforced composite materials.

Recently, an imide material having an ethynyl group or a mixed materialcomprising an imide compound having a diacetylene bond at the terminaland a dienophile compound has been investigated as a new curingmaterial, and possibilities of this new curing resin have been examined(see U.S. Pat. Nos. 4,311,601, 4,402,879 and 4,405,786). However, theelastic modulus of a cured shaped article of this curing resin is notsuperior to that of a cured shaped article of a conventional curingresin.

Separately, a fiber having a high elastic modulus has been manufacturedon an industrial scale by highly orienting a non-curable linear polymer.For example, there can be mentioned a gel-spun fibrous product ofpolyethylene and a liquid crystal-spun fibrous product ofpoly-p-phenylene terephthalamide.

In these materials, however, a high elastic modulus is manifested in theorientation direction but the elastic modulus is low in the directionrectangular to the orientation direction.

As an interesting example, there can be mentioned an investigation inwhich a whisker polymer close to a single crystal is synthesized bysolid-phase reaction of a diacetylene compound having urethane bonds,sulfonyl bonds or other bonds [see Polymer, 24, 1023 (1983); Journal ofPolymer Science, Polymer Physics Ed. 17, 569 (1979); and Report 1984(Order No. AD-A140912)]. However, as in case of the above-mentionedhighly oriented linear polymer, a high elastic modulus can be manifestedonly in one direction and it is impossible to manifest high strength andelastic modulus two-dimensionally or three-dimensionally.

SUMMARY OF THE INVENTION

It is the primary object of the present invention to provide a curablecompound which has a high reactivity and is capable of providing a curedshaped article having a high elastic modulus isotropically and excellentmechanical properties.

In accordance with the present invention, there is provided adiacetylene compound comprising, as structural units, (a) at least onemember selected from diacetylene group-containing organic groupsrepresented by the following general formulae (I) and (II):

    R.sup.I --C.tbd.C--C.tbd.C--R.sup.II --                    (I)

and

    --R.sup.III --C.tbd.C--C.tbd.C--R.sup.IV -- (II)

wherein R^(I) represents a hydrogen atom or a monovalent organic grouphaving 1 to 16 carbon atoms, and R^(II), R^(III) and R^(IV)independently represent a divalent organic group having 1 to 13 carbonatoms,

(b) at least one organic group having at least one carbon-to-carbondouble bond, and (c) at least one connecting group connecting thestructural units (a) and (b), which is selected from an amide bond, animide bond, an ester bond, an ether bond, an amino bond, an imino bond,a urethane bond, a sulfonyl bond and a carbonyl bond.

Furthermore, a shaped article made of the diacetylene compound mentionedabove is provided according to the present invention.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a partially cut-out sectional view of a molding machine usedfor making the compound of the present invention into a shaped article,and

FIG. 2 is a schematic diagram illustrating an isostatic pressureapparatus.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the present invention, R^(I) in the general formula (I) represents amonovalent organic group having 1 to 16 carbon atoms or a hydrogen atom.As examples of R^(I), there can be mentioned H--, CH₃ --, C₂ H₅ --, C₃H₇ --, (CH₃)₂ CH--, (CH₃)₃ C--, ##STR1## The organic group R^(I) maycontain a divalent connecting group such as an ether bond, an esterbond, an amide bond, an imide bond, an amino bond, an imino bond or aurethane bond. As examples of R^(I) of this type, there can be mentioned##STR2## Some or all of the hydrogen atoms of the organic group R^(I)may be substituted by a nitro group, a hydroxyl group, a cyano group, acarboxyl group, an amino group, a halogen atom or other substituents.

In the present invention, R^(II), R^(III) and R^(IV), which may be thesame or different, represent a divalent organic group having 1 to 13carbon atoms. For example, there can be mentioned aliphatic andalicyclic organic groups such as --CH₂ --, C₂ H₄ --,--C₃ H₆ --, ##STR3##Some or all of the hydrogen atoms of these organic groups may besubstituted by a nitro group, a hydroxyl group, a dyano group, acarboxyl group, an amino group, a halogen atom or other substituents.

The organic group R^(II), R^(III) and R^(IV) may have an ether bond, asulfonyl bond, an ester bond or a carbonyl bond. For example there canbe mentioned ##STR4##

R^(II), R^(III) and R^(IV) may be any of the foregoing groups. However,in view of the curing reactivity and the easiness of the synthesis,--CH₂ -- and ##STR5## are preferred.

In the present invention, the organic group (b) having at least onecarbon-to-carbon double bond is generally a monovalent or polyvalentorganic group having 1 to 20 carbon atoms and at least onecarbon-to-carbon double bond.

For example, there can be mentioned groups comprising at least onecarbon-to-carbon double bond and an aliphatic group, such as H₂ C═CH--,##STR6## and --CH₂ --HC═CH--CH₂ --; groups comprising at least onedouble bond and an aromatic group, such as ##STR7## groups having atleast one double bond included in a ring structure, such as ##STR8##

Some or all of the hydrogen atoms of these organic groups (c) may besubstituted by a nitro group, a hydroxyl group, a cyano group, acarboxyl group, an amino group, a halogen atom or other substituents.

Among these double bond-containing groups, in view of the reactivity,##STR9## preferred.

The diacetylene compound of the present invention comprises as anotherstructural unit a connecting group (c) connecting the above-mentioneddiacetylene group-containing organic group (a) and carbon-to-carbondouble bond-containing organic group (b). As the connecting group (c),there can be mentioned an ether bond --O--, ##STR10## The oxygen atomconstituting the connecting group may be substituted by a sulfur atom.Any of the foregoing connecting groups may be used. Furthermore, two ormore of the connecting groups, may be used in combination.

Among these connecting groups, in view of the balance between theprocessability and the curing reactivity, an amide bond, an ester bond,a sulfonyl bond, a carbonyl bond and an ether bond are preferred.Furthermore, an imide bond is preferred in view of the heat resistanceof the cured shaped article. An amide bond and an ester bond areespecially preferred.

The diacetylene compound of the present invention is a compound in whichthe above-mentioned diacetylene group-containing organic group (a) andcarbon-to-carbon double bond-containing organic group (b) are connectedin one molecule through the connecting group (c) . The numbers of thediacetylene group-containing organic group, carbon-to-carbon doublebond-containing organic group and connecting group present in onemolecule are not particularly critical. For example, the diacetylenecompound may be a compound containing one each of the foregoing groupsor a compound containing two or more of these groups. In the case wherethe diacetylene group-containing group, carbon-to-carbon doublebond-containing organic group and connecting group are contained asrepeating units, the units of each group may be the same or different.

In the diacetylene compound of the present invention, the ratio of thediacetylene group-containing organic group (a) to the carbon-to-carbondouble bond-containing organic group (b) is not particularly critical.In view of the curing reactivity, it is preferred that the molar ratioof the diacetylene group-containing organic group (a) to thecarbon-to-carbon double bond-containing group (b) be in the range offrom 0.2 to 5, and it is especially preferred that this molar ratio bein the range of from 0.5 to 2, because the curing reactivity is mostprominent and the elastic modulus of the cured shaped article is highlyimproved.

Examples of the diacetylene compounds of the present invention are asfollows: ##STR11##

Furthermore, there can be mentioned polymers comprising, for example,the following repeating units: ##STR12##

The diacetylene compound of the present invention can be synthesizedaccording to processes developed by modifying or improving known organicsynthesis processes.

For example, a diacetylene compound containing an amide bond as theconnecting group can be synthesized by polycondensing as the startingmaterial a diamine represented by the formula ##STR13## (in whichR^(III) and R^(IV) are as defined above and X and X' independentlyrepresent a hydrogen atom or an organic group) with a carboxylic acidhalide ##STR14## (in which R is an organic group having at least onecarbon-to-carbon double bond, and A represents a halogen atom), acarboxylic acid ester ##STR15## (in which R is as defined above and Brepresents an organic group) or a carboxylic acid ##STR16## (hereinafterreferred to as "process 1"), or by subjecting a diamide ##STR17## (inwhich R, R^(III) and R^(IV) are as defined above) to oxidative couplingpolymerization in the presence of a metal catalyst such as CuCl(hereinafter referred to as "process 2").

A diacetylene compound having an ester bond as the connecting group canbe synthesized by polycondensing a diol HO--R^(III)--C.tbd.C--C.tbd.C--R^(IV) --OH (in which R^(III) and R^(IV) are asdefined above) as the starting material with a carboxylic acid halide##STR18## (in which R is as defined above and A represents a halogenatom), a carboxylic acid ester ##STR19## (in which R is as defined aboveand B represents an organic group) or a carboxylic acid ##STR20## (inwhich R is as defined above) (hereinafter referred to as "process 1"),or by subjecting ##STR21## (in which R, R^(III) and R^(IV) are asdefined above) to oxidative polymerization in the presence of a metalcatalyst such as CuCl (hereinafter referred to as "process 2").

The synthesis process will now be described in detail with reference toa compound having an amide bond.

In the process 1 using, for example, a diamine ##STR22## and acarboxylic acid halide ##STR23## the diamine is dissolved in an alkalineaqueous solution, the carboxylic acid halide is dissolved in awater-immiscible organic solvent and the two solutions are mixedtogether. Moreover, the intended compound can be synthesized bypolycondensing the diamine ##STR24## with a carboxylic acid ester##STR25## or a carboxylic acid ##STR26## in an organic solvent in thehomogeneous system. In this case, if a homogeneous system is formed onlyby mixing the diamine with the carboxylic acid ester or carboxylic acid,the organic solvent need not be used. This polycondensation in thehomogeneous system can also be applied to the carboxylic acid halide.

In the process 2, the intended diacetylene compound can be synthesized,for example, by blowing oxygen into a solution (e.g., in pyridine) of aseparately synthesized diamide ##STR27## in the presence of a metalcatalyst such as CuCl.

In the process 1, the amount of the carboxylic acid halide, carboxylicacid ester or carboxylic acid to the diamine is not particularlycritical, but the amount is preferably 0.1 to 2 equivalents.

In the case of the above-mentioned process 1, the kind, concentrationand amount of the alkaline aqueous solution are not particularlycritical. The reaction temperature and reaction time also are notparticularly critical. However, it is generally preferred that thereaction temperature be -20° to 300° C. and the reaction time be 1minute to 10 hours.

In the oxidative polymerization in the above-mentioned process 2, it ispreferred that the amount of the metal catalyst used be 0.01 to 1 molarequivalent to the starting material and the flow rate of oxygen be 10 to1000 ml/min. Pyridine is preferred as the solvent used for the reaction,and other solvent may be present together with pyridine. The reactiontemperature and the reaction time are not particularly critical, but itis generally preferred that the reaction temperature be -20° to 100° C.and the reaction time be 20 minutes to 12 hours.

As the reaction for forming a diacetylene group, there can be adoptedthe Cadiot-Chodkiewicz coupling process in which a compound having anethynyl group is brominated and reacted with an other compound having anethynyl group. For example, this reaction is accomplished by adding anexcessive amount of an amine (for example, n-butylamine) and a catalyticamount of cuprous chloride to a solution of a compound having an ethynylgroup (for example, ##STR28## and gradually adding a compound brominatedethynyl group (for example, ##STR29## to the mixture with stirring. Inorder to control the occurrence of a side reaction, it is preferred thatthe amount of cuprous chloride be 1 to 5 mole %. Moreover, it isnecessary that a small amount of hydroxylamine be added.

Furthermore, there may be adopted a process in which an amino bond or aurethane bond is metallized and the metallized compound is reacted witha halide.

The shaped article of the present invention is obtained by shaping andcuring the diacetylene compound having at least one carbon-to-carbondouble bond. The form of the shaped article is not particularlycritical. For example, it can take any of a fibrous form, a filmy form,a sheet- or plate-like form, a membrane-like form, a tubular form, arod-like form and a powdery form according to need.

For the production of the shaped article of the present invention, therecan be adopted various molding methods such as compression molding,injection molding, rotational molding and molding from a solution ordispersion, and the molding method is not particularly critical. Curingis caused at the time of molding or before or after molding. By the term"curing", it is meant that a cured product is neither dissolved inordinary organic solvents nor fused, and it is generally considered thatcuring is effected by the crosslinking reaction.

As means for causing curing, there may be adopted application of heat,irradiation with light, compression and irradiation with radial rays orelectron beams singly or in combination. Application of heat andcompression are simple and effective.

For example, a compressed shaped article excellent in the heatresistance can be obtained by heating a powder of the diacetylenecompound without fusion, if necessary under gas compression.Alternatively, the compressed shaped article can be obtained bycompressing a powder of the diacetylene compound, if necessary underheating.

Furthermore, a cured film can be obtained by applying or spraying apowder or solution of the diacetylene compound onto a heated article.

Powder of the diacetylene compound of the present invention can beconveniently and effectively cured and molded by adopting heating meanstogether with rotational molding, injection molding, extrusion molding,rolling molding or the like.

In the case where the diacetylene compound of the present invention is apolymer or oligomer, combination of molding into a fiber or film withheat curing or with heat rolling or heat compression is preferred.

In the case where the diacetylene compound of the present invention ishighly crystallizable, there may be adopted a process in which a crystalis grown and the crystal is cured by heating or compression at atemperature lower than the melting point.

In producing the cured shaped article of the present invention,appropriate conditions for application of heat, compression or the likeare selected according to the properties of the diacetylene compound.For example, there may be adopted a method in which before molding, thedifferential thermal analysis is carried out to examine the temperaturerange where curing is effectively caused. The heating temperature isgenerally room temperature to 400° C. and preferably room temperature to350° C. In order to shorten the curing molding time in the industrialprocess, it is most preferred that the heating temperature be 30° to300° C. However, even if the heating temperature is lower than about250° C., curing is sufficiently advanced and the shaped article can beeasily produced.

Application of pressure is not indispensable but a reduced pressuresystem may be adopted in a certain method. However, if powder is shapedinto a body having a specific form, application of pressure is preferredand is utilized for promotion of curing. Generally, the pressure is atleast 0.5 MPa, and the upper limit is not particularly critical and apressure of up to the upper limit attainable in the industrial staticpressure technique may be adopted. Moreover, the impact pressure may beutilized. It is preferred that the pressure be 1 to 1,000 MPa,especially 5 to 700 MPa.

In the production of the shaped article, the diacetylene compound can bemixed with a thermosetting resin, a thermoplastic resin, an inorganicsubstance, a metal, a carbon material, a stabilizer, a flow modifier, aparting material, a colorant, an ultraviolet absorber, a curingpromotor, a curing inhibitor or the like. The form of the shaped articleis not limited to a powdery form, but the shaped body may have asheet-like form, a paper-like form, a fibrous form, a fleecy form, afibrous form, a granular form, a slice-like form, a plate-like form, arod-like form or a tubular form according to need.

The cured shaped article of the diacetylene compound according to thepresent invention has excellent mechanical properties. For example, theelastic modulus is at least 4 GPa, generally 5 to 8 GPa. If the kind ofthe diacetylene compound and the molding conditions are appropriatelyselected, an elastic modulus of about 10 GPa can be manifested.

In the present invention, the flexural modulus or the tensile moduluscan be adopted as the elastic modulus according to the form of theshaped article. As the standard method for determining the flexuralmodulus, there can be adopted the method of ASTM D790-66. However, theshaped article of the present invention is not limited to those whichhave a size (length) sufficient for the measurement according to themethod of ASTM D790-66. Accordingly, the following method is adopted formeasuring the flexural modulus of a small shaped article.

According to the method for measuring the flexural modulus, which isused in the present invention, the measurement is carried out by using atest specimen having a length of at least 15 mm, a width of 4 mm, and athickness of 2 mm, at a span (distance between the supports) of 10 mm, asupport nose radius of 2R, a loading nose radius of 5R and a crossheadrate of 5 mm/min. The value of the flexural modulus obtained accordingto this method as slightly smaller than but close to the value obtainedaccording to the method of ASTM D790-66.

The diacetylene compound of the present invention can be cured, forexample, at a temperature lower than 300° C., especially a temperaturelower than 250° C., and in a certain compound, curing is possible at atemperature lower than 100° C. The obtained shaped article has excellentmechanical properties. In ordinary organic polymers, the flexuralmodulus is 1 to 3 GPa. On the other hand, the cured shaped article ofthe present invention has a flexural modulus of at least 4 GPa andgenerally 5 to 8 GPa. In the case of a shaped article of a certaincompound included in the scope of the present invention, a flexuralmodulus of about 10 GPa is manifested.

The shaped article of the present invention is very useful forelectronic materials and precision machine parts.

The present invention will now be described in detail with reference tothe following examples that by no means limit the scope of theinvention.

EXAMPLE 1 ##STR30##

In 100 ml of a 5N aqueous solution of NaOH was dissolved 0.5 mole ofpropargylamine, the solution was mixed with a solution of 0.5 mole ofacryloyl chloride in chloroform, and the mixture was vigorously stirredat room temperature for 10 minutes. After the reaction was completed,the-chloroform layer was separated, and the residue was dried withanhydrous sodium sulfate to obtain ##STR31##

The thus-obtained product was stirred in pyridine in the presence ofcuprous chloride as the catalyst at room temperature for 2 hours underbubbling with oxygen at a flow rate of 500 ml/min. After the reactionwas completed, the precipitated product was isolated by filtration undersuction.

When the product was heated at a temperature-elevating rate of 20°C./min in nitrogen, exothermic phenomenon was observed (namely, curingoccurred) at 80° to 100° C. without melting. The elementary analysisvalues as C₁₂ H₁₂ N₂ O₂ were as follows.

    ______________________________________                                                    C     H        N       O                                          ______________________________________                                        Calculated values                                                                           66.7%   5.5%     13.0% 14.8%                                    Found values  66.6%   5.3%     13.1% 15.0%                                    ______________________________________                                    

In the IR absorption spectrum, characteristic absorptions were observedat 2170 cm⁻¹ (--C.tbd.C--), 1650 cm⁻¹ (amide bond) and 1580 cm⁻¹ (amidebond).

The compound was soluble in methanol, ethanol and ethyl acetate.

The product obtained by maintaining this compound at 200° C. for 1 hourin nitrogen was insoluble in methanol, ethanol and ethyl acetate.

EXAMPLE 2 ##STR32##

The reaction was carried out in the same manner as described in Example1 except that cinnamoyl chloride was used instead of acryloyl chloride.

When the product was heated at a temperature-elevating rate of 20°C./min in nitrogen, exothermic phenomenon was observed (namely, curingoccurred) at about 100° C. without fusion. The elementary analysisvalues as C₂₄ H₂₀ N₂ O₂ were as follows.

    ______________________________________                                                    C     H         N      O                                          ______________________________________                                        Calculated values                                                                           78.3%   5.4%      7.6% 8.7%                                     Found values  78.1%   5.6%      7.4% 8.9%                                     ______________________________________                                    

In the IR absorption spectrum of the compound, characteristicabsorptions were observed at 2170 cm⁻¹ (--C.tbd.C--), 1650 cm⁻¹ (amidebond) and 1580 cm⁻¹ (amide bond). The compound was soluble in acetone,methanol, ethanol and ethyl acetate.

When the compound was maintained at 200° C. for 1 hour in nitrogen, theproduct was insoluble in acetone, methanol, ethanol and ethyl acetate.

EXAMPLE 3 ##STR33##

In acetic acid, 0.165 mole (27.06 g) of 5-norbornene-2,3-dicarboxylicanhydride was reacted with 0.165 mole (9.1 g) of propargylamine inacetic acid under reflux. After the reaction was completed, the half ofacetic acid was evaporated from the solution, and the reaction mixturewas cooled and poured into water. The precipitate was isolated byfiltration under suction, and water washing was repeated until the smellof acetic acid disappeared, followed by drying under a reduced pressure(product A). A solution of 16.08 g of the product in pyridine wasdropped into a pyridine solution containing 0.08 mole (0.8 g) of cuprouschloride in a flask while bubbling with oxygen. After the reaction wascompleted, the solution was poured into water and the precipitate wasisolated by filtration. Water washing and was repeated, followed bydrying under a reduced pressure. A pale yellow powder was obtained. Theyield was 87.9% (14 g).

The melting point of the product was 190° to 193° C., and the elementaryanalysis values as C₂₄ H₂₀ O₄ N₂ were as follows.

    ______________________________________                                                    C     H         N      O                                          ______________________________________                                        Calculated values                                                                           72.0%   5.0%      7.0% 16.0%                                    Found values  72.0%   4.5%      6.8% 16.7%                                    ______________________________________                                    

In the IR absorption spectrum of the compound, characteristicabsorptions were observed at 2170 cm⁻¹ (--C.tbd.C--), 1770 cm⁻¹(5-membered ring imide) and 1720 cm⁻¹ (5-membered ring imide).

The solubility of the compound in a solvent was excellent. Namely, thecompound was soluble in acetone at room temperature and in methanol,ethanol and ethyl acetate under slight heating.

When the compound was heated, melting began at 190° C. and curing beganat about 210° C., and the compound was completely cured at about 250° C.Furthermore, when the compound was maintained at 210° C. for 5 minutes,the compound was completely cured. Moreover, at 200° C., curing wascompleted in 10 minutes. When the thermogravimetric analysis of thecured product was carried out in air, the weight loss was only 1.5% at450° C. Thus, it was confirmed that the heat resistance was veryexcellent.

EXAMPLE 4 ##STR34##

In the same manner as described in Example 3, 20 g (77% based on thetheoretical value) of a powder of a light yellow color was prepared from5-norbornene-2,3-dicarboxylic anhydride and aminophenylacetyleneobtained according to the process disclosed in Japanese UnexaminedPatent Publication No. 54-122,242.

The product was not fused up to 300° C. The elementary analysis valuesas C₃₄ H₂₄ O₄ N₂ were as follows.

    ______________________________________                                                    C     H         O       N                                         ______________________________________                                        Calculated values                                                                           77.9%   4.6%      12.2% 5.3%                                    Found values  78.0%   5.0%      11.8% 5.1%                                    ______________________________________                                    

In the IR absorption spectrum of the compound, characteristicabsorptions were observed at 2145 cm⁻¹ (--C.tbd.C--), 1770 cm⁻¹(5-membered ring imide) and 1715 cm⁻¹ (5-membered ring imide).

When the thermogravimetric analysis of the compound was carried out inair, the weight loss was only 1% at 470° C.

EXAMPLE 5 ##STR35##

In 200 ml of a 4N aqueous solution of NaOH was dissolved 0.5 mole of H₂N--CH₂ --C.tbd.C--C.tbd.C--CH₂ --NH₂, and 100 ml of a solution of 5 moleof ##STR36## in chloroform was gradually dropped into the alkalinesolution at 0° C. After the dropwise addition, white mass wasimmediately precipitated. The mixture was stirred for 30 minutes tocomplete the reaction. The formed polymer was isolated by filtrationunder suction. The yield was 96%. In the IR absorption spectrum (KBrmethod) of the polymer, characteristic absorptions were observed at 2960cm⁻¹, 1650 cm⁻¹ and 1580 cm⁻¹.

When differential thermal analysis (DTA) and thermogravimetric analysis(TGA) of the polymer were carried out in a nitrogen current at atemperature-elevating rate of 20° C./min, it was found thatdecomposition was not caused up to 200° C. The crosslinked polymerobtained by annealing the polymer at 180° C. for 5 hours was notthermally decomposed at 300° C. and thus showed a good heat resistance.

EXAMPLE 6 ##STR37##

The procedures of Example 5 were repeated in the same manner except that##STR38## was used instead of ##STR39##

In the IR absorption spectrum (KBr) of the product, characteristicabsorptions were observed at 3000 cm⁻¹, 1662 cm⁻¹ and 1583 cm⁻¹. Theproduct was soluble in N-methylpyrrolidone. When the product was heatedin nitrogen at a temperature-elevating rate of 20° C./min, exothermicphenomenon was observed at about 100° C. The product was renderedinsoluble in N-methylpyrrolidone when maintained at 130° C. for 3 hours.

EXAMPLE 7 ##STR40##

The procedures of Example 5 were repeated in the same manner except that##STR41## was used instead of ##STR42##

When the product was heated in nitrogen at a temperature-elevating rateof 20° C./min, exothermic phenomenon was observed (namely, curingoccurred) at about 90° C. without fusion.

EXAMPLE 8 ##STR43##

To a mixture of 1.5 moles of propargyl alcohol (HC.tbd.C--CH₂ --OH) and1.0 mole of Na₂ CO₃ was dropped 0.5 mole

of ##STR44## over a period of 10 minutes. The mixture became white massin about 1.5 hours after the dropwise addition. Water was added to thesolid and the precipitate was isolated by filtration under suction.Obtained ##STR45## was polymerized in pyridine as a solvent in thepresence of cuprous chloride under bubbling with oxygen.

The obtained polymer was soluble in N-methylpyrrolidone and hotdimethylsulfoxide. When the polymer was heated in nitrogen at atemperature-elevating rate of 20° C./min, absorption of heat by fusionwas observed at 110° to 140° C. Exothermic phenomenon by curing wasobserved at about 150° C.

In the IR absorption spectrum, characteristic absorptions were observedat 3287 cm⁻¹ (terminal H--C.tbd.) , 3082 cm⁻¹ ##STR46## 2130⁻¹(--C.tbd.C--) and 1720 cm⁻¹ (--COO--). The polymer was identified by ¹H-NMR and ¹³ C-NMR as well as IR.

The product obtained by maintaining the polymer at 160° C. for 3 hourswas insoluble in N-methylpyrrolidone and hot dimethylsulfoxide.

EXAMPLE 9 ##STR47##

This compound was subjected to the oxidative polymerization in the samemanner as in Example 8. The obtained polymer was soluble intetrahydrofuran. When the polymer was heated at a temperature-elevatingrate of 20° C./min in nitrogen, the polymer was softened at about 100°C., and a peak top of exothermic phenomenon appeared at 160° to 170° C.In the IR absorption spectrum, characteristic absorptions were observedat 2163 cm⁻¹ (--C.tbd.C--) and 1728 cm⁻¹ (--COO--). The polymer wasidentified by ¹ H-NMR and ¹³ C-NMR as well as IR. From the results ofgel permeation chromatography (GPC), it was estimated that the molecularweight of the obtained polymer was from several thousands to about100,000 as calculated as polystyrene. The product obtained by annealingthe polymer at 180° C. for 1 hour was insoluble in tetrahydrofuran.

EXAMPLE 10 ##STR48##

The procedures of Example 8 were repeated in the same manner except that##STR49## When the obtained polymer was heated in a nitrogen current ata temperature-elevating rate of 20° C./min, exothermic phenomenon bycuring reaction was caused at about 150° C. without fusion.

In the IR spectrum of the obtained compound, characteristic absorptionswere observed at 3288 cm⁻¹ (terminal H-C.tbd.), ##STR50## 2130 cm⁻¹(--C.tbd.C--) and 1720 cm⁻¹ (--COO--). The compound was identified by IRand elementary analysis.

EXAMPLE 11

The compound synthesized in Example 1 was molded into a rod-like articleby using the molding machine shown in FIG. 1 and the isostatic pressureapparatus shown in FIG. 2. Referring to FIG. 1, reference numeral 1represents a pushing rod, reference numeral 2 represents a pressingmember, reference numeral 3 represents a lid of a cylinder, referencenumeral 4 represents an outer cylinder, reference numeral 5 representsan air discharge pipe, reference numeral 6 represents an inner cylinder,reference numeral 7 represents a receiving plug, reference numeral 8represents a polymeric material, and each of reference numerals 9 and 10represents an O-ring. Referring to FIG. 2, reference numeral 11represents a hydraulic pump, reference numeral 12 represents a pressuregauge, reference numeral 13 represents a pressure vessel, referencenumeral 14 represents a band heater, and reference numeral 15 representsa high-pressure chamber.

Namely, the compound synthesized in Example 1 was packed in the cylinder4 of the molding machine shown in FIG. 1, and the inner pressure wasreduced by a vacuum pump. Subsequently, the molding machine was placedon a hydraulic press and compression molding was carried out under apressure of 30 MPa for 5 minutes at 30° C. Then, by using the isostaticpressure apparatus shown in FIG. 2, the molded article was treated underconditions shown in Table 1. The elastic modulus of the molded articlewas measured. The obtained results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Pressure                                                                             Temperature                                                            (MPa)  (°C.)                                                                             Time (hours)                                                                             Elastic Modulus (GPa)                            ______________________________________                                         50    23         1           9.4                                             100    23         1          10.0                                             300    23         1          11.2                                             300    50         1          11.3                                             300    100        1          13.2                                             650    23         1          12.0                                             650    50         1          12.4                                             650    100        1          14.0                                             650    150        1          14.3                                             ______________________________________                                    

EXAMPLE 12

A molded article shown in Table 2 was obtained by treating the compoundof Example 2 in the same manner as in Example 11.

                  TABLE 2                                                         ______________________________________                                        Pressure                                                                             Temperature                                                            (MPa)  (°C.)                                                                             Time (hours)                                                                             Elastic Modulus (GPa)                            ______________________________________                                         50    23         1          7.2                                              100    23         1          8.1                                              300    23         1          8.6                                              300    50         1          8.9                                              300    100        1          10.1                                             650    23         1          8.9                                              650    50         1          9.2                                              650    100        1          10.5                                             650    150        1          11.6                                             ______________________________________                                    

EXAMPLE 13

A molded article shown in Table 3 was obtained by treating the compoundof Example 3 in the same manner as in Example 11.

                  TABLE 3                                                         ______________________________________                                        Pressure                                                                             Temperature                                                            (MPa)  (°C.)                                                                             Time (hours)                                                                             Elastic Modulus (GPa)                            ______________________________________                                         50    200        1          6.6                                              100    200        1          7.2                                              ______________________________________                                    

EXAMPLE 14

A molded article shown in Table 4 was obtained by treating the compoundof Example 4 in the same manner as in Example 11.

                  TABLE 4                                                         ______________________________________                                        Pressure                                                                             Temperature                                                            (MPa)  (°C.)                                                                             Time (hours)                                                                             Elastic Modulus (GPa)                            ______________________________________                                        550    190        5          7.2                                              ______________________________________                                    

EXAMPLE 15

A molded article shown in Table 5 was obtained by treating the compoundof Example 5 in the same manner as in Example 11.

                  TABLE 5                                                         ______________________________________                                        Pressure                                                                             Temperature                                                            (MPa)  (°C.)                                                                             Time (hours)                                                                             Elastic Modulus (GPa)                            ______________________________________                                        400    150        2          10.8                                             650    100        1          15.0                                             650    150        2          15.2                                             650    200        1          16.6                                             ______________________________________                                    

EXAMPLE 16

A molded article shown in Table 6 was obtained by treating the compoundof Example 6 in the same manner as in Example 11.

                  TABLE 6                                                         ______________________________________                                        Pressure                                                                             Temperature                                                            (MPa)  (°C.)                                                                             Time (hours)                                                                             Elastic Modulus (GPa)                            ______________________________________                                        200    100        2           7.3                                             200    150        2           9.6                                             200    200        2          10.4                                             650    100        2           8.2                                             650    150        2          11.0                                             650    200        2          12.1                                             ______________________________________                                    

EXAMPLE 17

A molded article shown in Table 7 was obtained by treating the compoundof Example 7 in the same manner as in Example 11.

                  TABLE 7                                                         ______________________________________                                        Pressure                                                                             Temperature                                                            (MPa)  (°C.)                                                                             Time (hours)                                                                             Elastic Modulus (GPa)                            ______________________________________                                        200    100        2          10.0                                             200    150        2          12.8                                             200    200        2          13.9                                             650    100        2          13.9                                             650    150        2          14.3                                             650    200        2          15.6                                             ______________________________________                                    

EXAMPLE 18

A molded article shown in Table 8 was obtained by treating the compoundof Example 8 in the same manner as in Example 11.

                  TABLE 8                                                         ______________________________________                                        Pressure                                                                             Temperature                                                            (MPa)  (°C.)                                                                             Time (hours)                                                                             Elastic Modulus (GPa)                            ______________________________________                                         30    100        1           8.6                                              30    150        1          10.2                                              30    180        1          11.8                                             200    100        1           9.2                                             200    150        1          13.2                                             200    180        1          14.0                                             650    100        1          11.5                                             650    150        1          18.3                                             650    180        1          20.7                                             ______________________________________                                    

EXAMPLE 9

A molded article shown in Table 9 was obtained by treating the compoundof Example 9 in the same manner as in Example 11.

                  TABLE 9                                                         ______________________________________                                        Pressure                                                                             Temperature                                                            (MPa)  (°C.)                                                                             Time (hours)                                                                             Elastic Modulus (GPa)                            ______________________________________                                        200    100        1           7.4                                             200    150        1           9.8                                             200    200        1          10.5                                             650    100        1           8.4                                             650    150        1          11.3                                             650    200        1          12.4                                             ______________________________________                                    

EXAMPLE 20

A molded article shown in Table 10 was obtained by treating the compoundof Example 10 in the same manner as in Example 11.

                  TABLE 10                                                        ______________________________________                                        Pressure                                                                             Temperature                                                            (MPa)  (°C.)                                                                             Time (hours)                                                                             Elastic Modulus (GPa)                            ______________________________________                                        200    100        1           8.9                                             200    150        1          12.8                                             200    180        1          13.6                                             650    100        1          11.2                                             650    150        1          16.5                                             650    180        1          18.7                                             ______________________________________                                    

We claim:
 1. A diacetylene compound consisting of the structural units,(a) at least one member selected from the group consisting ofdiacetylene group-containing organic groups represented by the followinggeneral formulae (I) and (II):

    R'--C.tbd.C--C.tbd.C--R"--                                 (I)

and

    --R'"--C.tbd.C--C.tbd.C--R.sup.IV --                       (II)

wherein R' represents a hydrogen atom or a monovalent organic grouphaving 1 to 16 carbon atoms, and R", R'" and R^(IV) independentlyrepresent a divalent organic group having 1 to 13 carbon atoms, (b) atleast one organic group having at least one carbon-to-carbon doublebond, and (c) at least one connecting group connecting said structuralunits (a) and (b), said connecting group (c) is an ester bond.
 2. Adiacetylene compound as claimed in claim 1, wherein the molar ratio ofthe diacetylene derivative (a) represented by the formula (I) or (II) tothe double bond containing organic group (b) is in the range of from 0.2to
 5. 3. A diacetylene compound as set forth in claim 1, wherein R^(II),R^(III) and R^(IV) in the formulae independently represent --CH₂ -- or##STR51##
 4. A diacetylene polymer consisting of the structuralunits,(a) at least one member selected from the group consisting of adiacetylene derivative of formula (I):

    R'--C.tbd.C--C.tbd.C--R"--                                 (I)

and a diacetylene derivative of formula (II)

    --R'"--C.tbd.C--C.tbd.C--R.sup.IV --                       (II)

wherein R' is selected from the group consisting of --CH₃, --C₂ H₅, and##STR52## R", R'" and R^(IV) independently represent a divalenthydrocarbon group selected from the group consisting of --CH₂ --,##STR53## (b) at least one organic group having at least onecarbon-to-carbon double bond selected from the group consisting of:##STR54## (c) at least one connecting group bonded directly to an openvalence of each of said structural units (a) and (b), wherein saidconnecting group (c) is an ester group; and (d) at least one chainterminating group, wherein said chain terminating group is bondeddirectly to an open valence of structural units (a), (b) and (c) andwherein the chain terminating group (d) is selected from the groupconsisting of ##STR55##